Supersensitization of meso-aryl carbocyanine dyes



Das., E29 i195@ E. H. CARRQLL, 2533,42?

SUPERSENSITIZATION OF MESO-ARYL CRBOCYANINE DYES Filed July 13, 1949 .300 40o 50a 60o 70mm# B URT H. CARROLL I N VEN TOR ATTORNEY AGENT Patented ec. 12, 1950 SUPERSENSITIZATION F MESO-ARYL CARBOCYANINE DYES Burt H. Carroll, Rochester, N. Y., assigner to Eastman Kodak Company, Rochester, N. Y., a corporation of New Jersey Application July 13, 1949, Serial No. 104,567

18 Claims. (Cl. 95-7) This invention relates to photographic emulsions comprising mese-aryl carbocyanine dyes and as supersensitizers therefor, hemicyanine dyes.

It is known in the artof making photographic emulsions that certain dyes of the cyanine class alter the sensitivity or" photographic emulsions of the gelatine-silver kind, when the dyes are incorporated in the emulsions. It is also kno-.vn that the sensitization produced by given dye varies somewhat with the type of emulsion in which the dye is incorporated. Furthermore, the sensitization of a given emulsion by a given dye may be altered by varying conditions in the emulion. For example, the sensitization may be increased by increasing the silver ion concentration or decreasing the hydrogen ion concentration (i. e. increasing the alkalinity) or both. Thus, sensitization can be increased by bathing plates, coated with a spectrally sensitized emulsion, in water or in aqueous solutions of ammonia. Such a process of altering the sensitivity of a sensitized emulsion increasing the silver ion concentration and/ or by decreasing the hydrogen ion concentration is commonly called hypersensitization 'Hypersensitized emulsions have generally poor keeping qualities.

More recently, it has been found that the sensitization produced in an emulsion by certain cya-nine dyes, particularly monomethine cyanine dyes, can be increased by incorporating in the sensitized emulsion certain hernicyanine dyes, particularly hemidicarbocyanine dyes (U. S. Patent 2,218,230, dated October 15, i940). Inasniuch as conditions in the emulsion, i. e., the silver ion and/ or the hydrogen ion concentration undergo little or no change in such a method, the phenomenon has been called supersensitization.

I have now found a new means of altering the Sens "y in emulsions containing certain other cyanine dyes of a particular type. Since the conditions in the emulsion, i. e., the hydrogen ion and/or the silver ion concentration undergo little or no change in my new method, l shall designate my new method as a kind or supersensitization. My new method is not to be confused with the method described in U. S. Patent 2,218,230, wherein cyanine dyes dierent from those utilized in this invention have their sensitivity altered with hemicyanine dyes, particularly hemidicarbocyanine dyes. Many of the dyes supersensitized `ccording to the method of U. S. Patent 2,218,230 are excellent sensitizers in their own right, whereas many oi the dyes supersensitized according to the present invention are relatively poor sensitizers in their own right. it was, therefore, most unexpected to iind that the cyanine dyes useful in practicing my invention could advantageously be supersensitized with hernicarbooyanine dyes.

It is, therefore, an object of my invention to provide photographic emulsions comprising certain cyanine dyes and, as supersensitizers therefor, certain hemicarbocyanine dyes. A further object is to provide a process for preparing these supersensitized emulsions. Other objects will become apparent from a consideration of the following description and examples.

The cyanine dyes useful in practicing my invention are the carbocyanine dyes containing an aryl group in the meso, or central, position of the intercyclic chain. Such dyes can advantageously be represented by the following general formula:

wherein R and R1 each represents an alcohol radical (i. e. an alkyl group, substituted or unsubstituted) e. g., methyl, ethyl, n-propyl, n-butyl, isobutyl, etc. groups, D represents an aryl group, e. g. phenyl, oand p-chlorophenyl, o, rn-, and p-tolyl, etc. groups, Z and Zi each represents the non-metallic atoms necessary to complete a heterocyclic nucleus selected from those of the benzothiazole series, those of the -naphthothiazole series and those of the benzoselenazole series and X represents an anion, such as halide (e. g. bromide, chloride, iodide), niethylsulfate Cl-I3SO4-) ethylsulfate (CzHsSOi-l benzenesulfonate, p-toluenesulionate, perchlorate, thiocyanate, etc.). The dyes represented by the above forinula can advantageously be prepared by methods described in U. S. Patents 1,984,659 (dated November 7, 1933), 2,369,646 (dated February 20, 1945) and 2,369,657 (dated Februar",7 20, 1945).

The hemicarbocyanine dyes useful as supersensitizers according to the method of rny invention can advantageously be represented by the following general formula:

wherein Re represents an alcohol radical (i. e. an alkyl group, unsubstituted and substituted) e. g. methyl, ethyl, n-butyl, isobutyl, etc. groups, X1 represents an anion such as halioe (e. g. bromide, chloride, iodide), methylsulate ethylsulfate (C2H5SO4-), benzenesulfonate, ptoluenesulionate, perchlorate, tl'lioeyanate,` etc.) L represents a inethenyl group, such as CH or substituted methenyl, (e. g. '-,vherein R3 is a methyl or ethyl group), J represents a hydrogen atom or an alkyl group (e. methyl, ethyl, etc. groups), Q represents an alkyl group (e. g. methyl, ethyl, etc. groups), an aryl group (e. g. a phenyl group, an alkoxyphenyl group, a -naphthyl group, etc.) or J and Q together represent the non-metallic atours necessary to complete a heterocyclic nucleus other than a nucleus of the pyrrol series, and Z2 represents the non-metallic atoms necessary to complete an organic heterocyclic nucleus. These hernicarbocyanine dyes have little (if any) sensitizing eect when used alone as sensitizers for photographic silver halide emulsione. It was, therefore, surprising to nd that the combination of such hemicarbocyanine dyes with mese-aryl cyanine dyes, which are themselves relatively weak sensitizers, provided elective means for advantageously' altering the sensitivity of photographic silver halide emulsions.

Many of the hemicarbocyanine dyes useful in practicing my invention have previously been described in U. S. Patents 2,166,736, dated July 18, 1939, 2,218,236, dated October 15, 19410, 2,263,- 749, dated November 25, 1941', 2,298,732, dated zothiazole, benzoxazole, benzoselenazole, ,e-naphthothiazole and Quinoline alkyl Quaternary salts, e. g.:

2- [2-(1-piperidyl) -l-butenyll benzothiazole methand ethiodides, etc.

(D) The 2-[2-(N-arylamino) vinyl] benzothiazole, benzoxazole, benzoselenazole, -naphthothiazole and Quinoline alkyl Quaternary salts,

Z-(-anilino) vinylbenzothiazole methand ethiodides,

, 2-(-ani1ino) viylbenzxazole niethand ethiodides, etc.

(E) The Z-[Z-(N-arylamino) propenyll benzothiazole, benzoxazole, benzoselenazole, -naphthothiazole and Quinoline alkyl Quaternary salts,

2-[2-(p-chlor`anilino) propenyll benzothiazole methand ethiodides,

2-(2-anilino) propenyl--naphthothiazole meth- October 13, 1942, and 2,301,361, dated November Typical hemicarbocyanine dyes useful in prac'- ticing my invention are those selected from the i" (B) The 2-[2-(1-piperidyl)propenyll benzothiazole, benzoxazole, benzoselenaaole, -naprhthothiazole and quinoline alkyl Quaternary salts,

2- [2-(1-piperidyl) propenyll benzothiazole,

methand ethiodides, etc. Y

(C) The 2-[2-(1-piperidyl)-l-butenyll benand ethiodides, etc.

(F) The 2-[2-(N-arylamino) -l-butenyll benzothiazole, benzoxazole, b'enzosel'en'azole, -naphthothiazole and quinoline alkyl Quaternary salts, e. g.:

2- [2- (p-anisidino) -l-butenyll benzothiazole methand ethiodides, 2-(2-anilino) -1-butenylquinoline ethiodides, etc.

methand (G) rhe 2-(2-dialkylaminovinyl) benzothiazole, benzoxazole', benzoselenazole, -naphthothiazole and Quinoline alkyl Quaternary salts, e. g.:

2-(-dimethylaminovinyl) benzothiazole methoand eth0-p-toluenesulfonates 2-(-diethylaminovinyl) benzoselenazole methand ethiodides, etc.

2 (.2 dimethylaminopropenyl) benzothiazole methoand ethobromides, 2 (2 dimethylaminopropenyl) benzoxazole methand ethiodides, etc.

(I) The 2-[2-(dialkylamino) -l-butenyll benzothiazole, benzoxazole, benzoselenazole, -naphthothiazole and Quinoline alkyl Quaternary salts,

2- [2- (dimethylamino) -l-butenyll benzothiazole methand ethiodides, etc.

(J) The 2-l2-(4-morpho1inyl) vinyl] benzothiazole, ben'zoxazole, benzoselenazole, -naphthothiazole and Quinoline alkyl Quaternary salts,

2-[-(4-morpholinyl) vinyl] benzothiazole methand ethiodides,

2- (l-morpholinyl) vinyl] methoand ethobromides, etc.

benzoselenazole (K) The 2-[2-(4-morpholinyl) propenyll benzothiazole, benzoxazole, benzoselenazole,

'assainir salts, e. g.':

2-[2-(4-morpholinyl) propenyll benzothiazole Anaphthothiazole and quinoline alkyl quaternary salts, e. g.:

benzoxazole l centration of the meso aryl carbocyanine'dyes Which I employ in practicing my invention, is of the order of 0.05 to 0.25 g. per mole of silver 2- [2-(4-morpholinyl) -l-butenyll benzothiazole methand ethiodides, etc.

(M) The 2-[2-(N-alkyl-N-arylamino) vinyl] benzothiazole, benzoxazole, benzoselenazole, naphthothiazole and quinoline alkyl quaternary salts, e. g.:

Z-[-(N-methylanilino) vinyl] benzothiazole methand ethiodides, etc.

According to my invention, I incorporate one or more of the cyanine dyes selected from those yrepresented by Formula I above with one or more of the hemicarbocyanine selected from those vrepresented by Formula II above in a photographic emulsion. My invention is particularly directed to the ordinarily employed gelatinesilver-halide emulsions. However, my supersensitizing combination can be employed in sillver halide emulsions in which the carrier is other than gelatin, e. g. a resinous substance or cellulosic material which has substantially no deleterious eiiect on the light-sensitive mate rials.

The sensitizing dyes can be employed in various concentrations depending upon the eiects desired. As is well known in the art, the sensitivity conferred upon an emulsion by a sensitizing dye does not increase proportionately to the coni The optimum concentration of an individual sensitizing dye can be determined in a manner well known to those skilled in the art by measuring the sensitivity of a series of test portions of the same emulsion, each portion containing a different concentration of the sensitizing dye. TheY optimum concentration of my supersensitizing combinations can, of course, be readily determined in the same manner, by meas'- uring the sensitivity of a series of test portions of the same emulsion, each portion containing different concentrations or" the individual dyes in the combination. In Vdetermining the optimum concentration for the supersensitizing combination, it is advantageous to employ, at first, concentrations of the individual dyes less than their optimum concentrations. The concentrations ol the individual dyes can then be increased until th optimum concentration oi the .siipcrsensitizing combination is determined.

Ordinarily the optimum or near optimum conhalide in the emulsion.

The hemicarbocyanine dyes utilized in my invention are advantageously employed at concentrations on the order of 0.05 to 0.25 g.per mole of silver halide in the emulsion.

Generally speaking, the ratio of concentration of a hemicarbocyanine dye (Formula II) to carbocyanine dye (Formula I) can vary rather widely in my new combinations, e. g. from 5:1 to 1:5 (by weight) lin many cases.

The methods of incorporating sensitizing dyes in emulsions are well known to those skilled in the art. In practicing my invention, `the sensitizing dyes can be incorporated in the emulsions separately or together. It is convenient to add the dyes separately in the form of solutions in appropriate solvents. Methanol and ethanol, especially thel former, have proven'satisiactory as solvents for the .dyes which I employ. The dyes are advantageously incorporated in the finished, washed emulsions and should be uniformly distributed throughout the emulsions. The following procedure is satisfactory: Stock solutions of the sensitizing dyes desired are prepared by dissolving the dyes in methyl or ethyl alcohol. Then, to one liter of a owable gelatino-silver-halide emulsion, the desired amounts of the stock solution of one of the .dyes (diluted somewhat with water, if desired) is slowly added, while stirring the emulsion. Stirring is continued until the dye is thoroughly incorporated in the emulsion. Then y the desired amount of the stock solution of the second dye (diluted somewhat with water, if ole'- sired) is slowly added to the emulsion, while stirring. stirring is continued until the second dye is thoroughly incorporated. The supersensitized emulsion can then be coated out on a suitable support, such as glass, cellulose derivative iilm, resin lilm, or paper, to a suitable thickness and allowed to dry. The details of such coating methods are well known to those skilled in the art.

The amounts of the individual sensitizi'ng .dyes actually incorporated in the emulsion will vary somewhat from dye to dye, according to the emulsion employed and according to the effect desired. The regulation and adoption of the most economical and useful proportions will be apparent to those skilled in the art upon making the ordinary observations and tests customarily employed Iin the art. Accordingly, the foregoing procedures and proportions are to be regarded only as illustrative. Clearly my invention is directed to any emulsion containing a combination of the aforesaid sensitizing dyes whereby a supersensitizing effect is obtained.

The following examples will serve to illustrate further the manner of practicing my invention. To different portions of the same batch of photographic gelatino-silverbromiodide emulsion were added (l) a carbocyanine dye selected from those represented by Formula I above and 2) a combination of the carbocyanine dye and a hemicarbocyanine dye selected from those represented by Formula II above. The diiierent portions of emulsion were then coated on glass supports and exposed in the usual manner in a spectrograph and in a sensitometer to white light and through lters, including a Wratten No. 25 lter,i. e. a lter which transmits substantially no light of Wavelength shorter than 580 mu. Following are several examples of such emulsion together with the speed (clear or white light and red), gamma and fog obtained.

`The heterocyclic nuclei of the dyes selected from those represented by Formulas I and II White Light Exposure Red Light Exposure Example Dye (g. per mole oi silver halide in emulsim) Speed Gamma Fo" Speed Gammo Fog 1 (a) 3,3'-diniethyLQ-phenyl-d,5,4,5-dibenzothincarbocyanine bromide (0.077) 34. 0 5. l0 .08 16. 2 5. 60 08 (b) dye (a) (0.077) with 2-(2aniliuo1butenyl)-B-ndphthothiazole methiodide 66. 0 5. 30 .09 40. 0 5. 55 09 7 2 (c) dye (a) (0.077),... 34.0 5.10 .08 16.2 5.00 .08 (d) dye (a) (0.077) with 2[2(p-chloroanilino-l-butenylj--naphthothiszole 98. O l. 70 10 65.0 5. 65 10 methiodide (0.077). 3 (e) dye (a) (0.078)- l 1380 1.23 .10 105 .25 .10 (j) dye (a) (0.078) with 2- p-chlorosnilino)-l-butenyl]naphthothiazole 1200 1. 45 10 300 1. 55 10 methiodide (0.078). f1 (g) ldimethylephenylselenacarbocyanine bromide (0.086) 42. 0 3. 77 05 4. 80 3. 93 05 (h) dye (y) (0.086) with 2Bnni1inovinylqiiinoline e iodide (0.086). 01. 0 S. 44 04 8. 80 3. 72 04 5 (i) dye (a) (0.078) Y.... 1380 1.23 .10 105 1.25 .10 (j) dye (a) (0.078) with 2'[2-(p-chloroenilino)propenyl] benzothiazolc ethio- 1350 l. 33 l0 230 1. 27 10 dide (0.078). d (la) dye (Il) (0.078) ....Y.. 1380 1. 23 .10 105 1.25 .10 (l) dye (a) (0.078) with 2-(p-anisidinovinyl)-5-ehlerobenzothiazole etho-p- 1080 1. 20 14 255 1.05 14 toluene-sulfonate (0.078). dye (g) (0.086) ...7...... 42.0 3.77 .05 4.80 3. 93 .05 dye (g) (0.086) with 2-[2-(p-anisidino)propenyl] benzfn hiazole ethiodide 46. 0 3. 42 .05 5. 50 3. 43 .05

.0S dye (a) (0.0755). Y A e... r; 1380 1.23 .10 105 1.25 .1() dye (a) (0.078) with 2-[2-(1piperidy1)vinyl] benzothiszole ethiodide (0.078) 1380 1. 5l l0 220 1. 62 10 dye (a) (0.07 1380 1. 23 .10 165 1. 25 .10 dye (a) (0.078) with 2-{..f(1piperid5y vinyl] quinoli'ne cthiodide (0.078) 1900 1. 18 10 225 1.39 10 dye (a .078) 1380 1. 23 .10 105 1.25 .1() dj: (u) (0.078) with 2-l2-(l-p" crid'yDviuyl] ben uzole ethiodde (0078).. 1. 28 .10 185 1.43 .l0 3,3dimethyl-9-phony1thiacsrboeyaninc iodide (0.086)` 40. 0 3.40 .o5 4. S0 3. 49 .05 dye (u) (0.080) with Z-B-anilinovinylquiuoline ethiedide (0.036). 50. 0 3. 78 .05 0. S0 3.51 05 dye (Il) (0.078) 1. 22 .10 105 1. 25 10 dye (u) (0.078) with 2-["-(pchlorozmilino)-l-butenyl] benzosclennzole 1230 1. 40 0B 205 1.47 .08

ethiodido (0.078) a (HZ-chlorophenyl-3,3dimethyl-4,54',5dibenzothiacarbocyunme bromide 23. 5 4. 25 .05 7. 10 6.00 0 n 0.077). dye (1l) (0.077) with 2-(2anilino-l-butenyl)=nnphthothiazole niethiodide 44. 0 4. 00 10 28. O 4. 75 10 .077 y 14 (11') dye (u) (0.078) 100 2. 92 .05 12.3 3.30 .05 (b) dye (u) (0.078) with 2-[2-(p-chlorosniiino)-l-huteny1]naphthothiazo1e 110 2. 86 04 21. 5 3.32 0i mcthiodide (0.078).

In the manner described above still many other supersensitizing combinations of one or :more of the mese-aryl carbocyanine dyes selected from those represented by Formula I above with one or more of the hemicarbocyanine dyes selected from those represented by Formula II above can be prepared.

The mese-aryl carbocyanine dyes useful in practicing my invention are well known in the art. Especially useful are the:

bocyanine bromide.

(B) 9aryl-3,3dialkylthiacarbecyanine salts,

3,3'diethyl-9-phenyltiiiacarbocyanine bromide.

(C) 9aryl3,3-dialkylselenacarbocyariine salts,

3,8 -dimetnyl-9-phenylselenacarbocyanine bromide.

3,3 dimethyl-9phenyl4,5benzothiathiacarbo cyanine bromide.

(E) 9-aryl3,3-dialkyl-4,5-benzotliiaselenacarbocyanine salts, e. g.:

3,3'dimethyl-9-phenyl-e benzothiaselenacarbocybocyanine bromide.

(F) aryl-3,23'-diallsylthiaselenacarbecyanine salts, e. g.:

3,3dimethyl 9 phenylthiaselenacarbocyanine bromide.

above, and the aryl nucleus represented by D above can be substituted by simple substituents which do not interfere with sensitizing properties, e. g. alkyl (e. g. methyl, ethyl, etc.) alkoxyl (e. g. methoxyl, ethoxyl, etc.) or chloro groups.

The accompanying drawing illustrates the supersensitizing elect obtained with three of my new combinations in silver bromiodide emulsions. Each figure of the drawing is a diagrammatic reproduction of two spectrograms. In each figure the sensitivity of the emulsion containing only the mese-aryl carbocyanine dye is represented by the lower curve. The upper curve represents the sensitivity conferred on the emulsion by the cornbination of the mese-aryl carbocyanine dye and the hemicarbocyanine dye. No curve showing the sensitivity conferred on the emulsion by the hemicarbocyanine dye alone is shown, since the sensitivity conferred by the hemicarboeyanine dye in question is too weak to be signicant in the comparisons shown.

In Figure 1, curve A represents the sensitivity of an ordinary gelatine-silver-bromiodide emulsion sensitized with 3,3'-dimethyl-Q-phenylselenacarbocyanine bromide, and curve B represents the sensitivity of the saine emulsion containing 3,3 dimethyl 9 phenylselenacarbocyanine bromide and 2-[2-(p-anisidino) propenyl] benzothiazole ethiodide. The sensitometric measurements for these emulsions are given in Example 7 of the above table.

In Figure 2, curve C represents the sensitivity of an ordinary gelatino-silver-bromiodide emulsion sensitized with 3,3-dimethyl-Q-phenylthiacarbocyanine iodide, and curve D represents the sensitivity of the same emulsion containing 3,3- dimethyl-9-phenylthiacarbocyanine iodide and 2--anilinovinylquinoline ethiodide. The sensitometric measurements for these emulsions are given in Example 11 of the above table.

In Figure 3, curve E represents the sensitivity of an ordinary gelatino-silver-bromiodide emulsion sensitized with 3,3'-dimethyl-Q-phenylselenacarbocyanine bromide, and curve F represents the sensitivity of the same emulsion containing 3,3 dimethyl-9phenylselenacarbocya nine bromide and Z--anilinovinylquinoline ethiodide. The sensitometric measurements for these emulsions are given in Example 4 of the above table.

My invention is primarily directed to the ordinarily employed gelatino-silver-halide developing-out emulsions, e. g. gelatinosilverchloride, -chlorobromide, -chloriodide, -chlorobromiodide -bromide and -bromiodide developing-out emulsions. While the results in the above table were obtained using gelatino-silver-bromiodide emulsions, excellent results have also been obtained using gelatino-silver-chlorobromide emulsions.

Emulsions which form the latent image mostly inside the silver halide grains, such as the emulsion set forth in U. S. Patent 2,455,956, dated December 21, 1948. can also be employed in practicing my invention.

The emulsions prepared in accordance with my invention can be coated in the usual manner on any suitable support,l e. g. glass, cellulose nitrate lm, cellulose acetate nlm, polyvinyl acetal resin lm, paper or metal.

What I claim as my invention and desire secured by Letters Patent of the United States is:

1. A photographic silver halide emulsion sensitized with a supersensitizing combination of at least one mesoaryl carbocyanine dye selected from those represented by the following general formula:

wherein R and R1 each represents an alkyl group of the formula CnHinm wherein n represents a positive integer from 1 to 4, D represents a monocyclic aryl nucleus oi the benzene series, X

represents an acid radical, and Z and Z1 each represents the non-metallic atoms necessary to complete a heterocyclic nucleus selected from those of the benzothiazole series, those of the ,8-naphthothiazole series and those of the benzoselenazole series, and at least one hemicanbocyanine dye selected from those represented by the following general formula:

wherein Re represents an alkyl group of the formula CnH2n+1 wherein 'n represents a positive integer of from l to 4, L represents a meth-any1 group, X1 represents an acid radical, Z2 represents the non-metallic atoms necessary to complete an organic heterocyclic nucleus selected from those of the benzothiazole series, those of the benzoxazole series, those of the benzoselenazole series, those or the -naphthothiazole series and those of the quinoline series, J represents a 'member selected from the group consisting of a hydrogen atom and an alkyl group of the formula Calderara wherein d represents a positive integer from l to 2, Q represents a member selected from the group consisting of alkyl ,group ci the formula Cslfizam, wherein d represents a positive integer from l to 2, and a mono-cyclic,

laryl group of the benzene series, and J and Q together represent the non-metallic atoms necessary to complete an organic basic nucleus selected from the group consisting of those of the piperidyl series and those of the morpholinyl series.

2. A photographic gelatino-silver-halide developing-out emulsion sensitized with a supersensitizing combination of at least one mese-aryl carbocyaninedye selected from those represented by the following general formula:

wherein R2 represents an alkyl group of the rormula CnHzni-l wherein n represents a positive integer of from 1 to 4, L represents a methenyl group, X1 represents an acid radical, Z2 represents the non-metallic atoms necessary to complete yan organic heterocyclic nucleus selected from those of the benzothiazole series, those of the benzoxazole series, those of the benzoselenazole series, those of the -naphthothiazole series and those of the quinoline series, J represents a member selected from the group consisting of a hydrogen atom and an alkyl group of the formula Cdl-izan wherein d represents a positive integer from l to 2, Q represents a member selected from the group consisting of an valkyl group of the formula Cdlzfzm wherein d represents a positive integer from 1 to 2, and a monocyclic aryl group of the benzene series, and J and Q together represent the non-metallic atoms necessary to complete an organic basic nucleus selected from the group consisting of those of the piperidyl series and those of the n1 orpholinvl series.

3. A photographic gelatine-silver-bromiodide developing-out emulsion sensitized with a supersensitizing combination of at least one meso-aryl carbocyanine dye selected from those represented by the following general formula:

wherein R and R1 each represents an alkyl group of the formula Callian wherein n represents a positive integer from 1 to 4, D represents a mono cyclic aryl nucleus of the benzene series, X represents an acid radical, and Z and Z1 each represents the non-metallic atoms necessary to complete a heterocyclic nucleus selected from those of the benzothiazole series, those of the -naphthothiezole series and those of the benzoselenazole series, and at least one hemicarbocyanifle dye 'l s 1 i; selected from those represented by the following general formula:

wherein Rz represents an alkyl group of the formula C11H2n+1 wherein n represents a positive integer of from l to s, L represents a methenyl group, X1 represents an acid radical, Z2 represents the non-metallic atoms necessary to complete an organic heterocyclic nucleus selected from those ci" the benzothiazole series, those of the benzoxazole series, those of the benzoselenazole series, those of the -naphthothiazole series and those of the quinoline series, J represents a member selected from the group consisting of a hydrogen atom and an alkyl group of the formula CdHQdJfi wherein d represents a positive integer from l to 2, Q represents a member selected from the group consisting of an alkyl group of the formula Cdl-Isdn wherein d represents a positive integer from 1 to 2, and a monocyclic aryl group of the benzene series, and J and Q together represent the non-metallic atoms necessary to complete an organic basic nucleus selected from the group consisting of those of the piperidyl series and those of the morpholinyl series.

4. A photographic gelatino-silver-halide developing-out emulsion sensitized with a supersensitizing combination of at least one mese-aryl car bocyanine dye selected from those represented by the following general formula:

.zg J l \I` C-L=L-N wherein R2 represents an alkyl group of the for- .mula C11H2n+1 wherein n represents a positive integer of from 1 to 2, L represents a methenyl group, X1 represents an acid radical, Zz represents the non-metallic atoms necessary to complete an organic heterocyclic nucleus selected from those of the benzothiazole series, those of the benzoxezole series, those of the benzoselenazole series, those of the ,B-naphthothiazole series and those of the quinoline series, J represents a member selected from the group consisting of a hydrogen atom and an alkyl group of the formula Cal-121144 wherein d represents a positive integer from 1 to 2, Q represents a member selected from the group Censis-,tinrvr of an alkyl group of the iormula CaHzfwi wherein d represents a positive integer from l to 2, and a monocyclic aryl group of the benzene series, and J and Q together represent the non-metallic atoms necessary to complete an organic basic nucleus selected from the group 12 consisting of those of the piperidyl series and those of the morpholinyl series.

5. A photographic gelatino-silver-halide developing-out emulsion sensitized with a supersensitizing combination of at least one meso-aryl carbocyanine dye selected from those represented by the following general formula:

vherein R2 represents an alkyl group of the formula CnH2n+1 wherein n represents a positive integer of from 1 to 2, L represents a methenyl group, X1 represents an acid radical, Zz represents the non-metallic atoms necessary to complete an organic heterocyclic nucleus selected from those of the benzothiazole series, those of the benzoxazole series, those of the benzoselenazole series, those of the -naphthothiazole series and those of the quinoline series, J represents a member selected from the group consisting of a hydrogen atom and an alkyl group of the formula CdHzdl-i wherein d represents a positive integer from 1 to 2, represents a member selected from the group consisting of an alkyl group of the formula. C11H2z+1 wherein d represents a positive integer from 1 to 2, and a monocyclic aryl group of the benzene series, and J and Q together represent the non-metallic atoms necessary to complete an organic basic nucleus selected from the group consisting of those of the piperidyl series and those of the morpholinyl series.

6. A photographic gelatino-silver-halide developing-out emulsion sensitized with a supersensitizing combination of at least one mesoaryl carbocyanine dye selected from those repsented by the following general formula:

wherein R and R1 each represents an alkyl group of the formula CnHzn-H wherein n represents a positive integer from 1 to 2, D represents a, monocyclic aryl nucleus of the benzene series, X represents an acid radical, and Z and Z1 each represents the non-metallic atoms necessary to complete a heterocyclic nucleus of the benzothiazole series, and at least one hernicarbocyanine dye selected from those represented by the following general formula:

wherein R2 represents an alkyl group of the formula CnHznM wherein n represents a positive integer of from 1 to 2, L represents a methenyl group, X1 represents an acid radical, Z2 represents the non-metallic atoms necessary to complete an organic heterocyclic nucleus selected from those of the benzothiazole series, those of the benzoxazole series, those of the benzoselenazole series, those of the -naphthothiazole series and those of the quinoline series, J represents a member selected from the group consisting of a hydrogen atom and an alkyl group of the formula CdHzfiJfi wherein d represents a positive integer from 1 to 2, Q represents a member selected from the group consisting of an alkyl group of the formula Cdl-Inni wherein d represents a positive integer from 1 to 2, and a monocyclic aryl group of the benzene series, and J and Q together represent the non-metallic atoms necessary to complete an organic basic nucleus selected from the group consisting of those or the piperidyl series and those of the morpholinyl series.

v7. A photographic gelatino-silver-halide developing-out emulsion sensitized with a supersensitizing combination of at least one mesoaryl carb-ocyanne dye selected from those represented by the following general formula:

Zim I cut-:IFN

wherein. R2 represents an alkyl group of the formula Cal-Irun wherein n represents a positive integer of from 1 to 2, L represents a methenyl group, X1 represents an acid radical, Z2 represents the non-metallic atoms necessary to complete an organic heterocyclic nucleus selected from those cf the benzothiazole series, those of the benzoxazole series, those of the benzoselenazole series, those ci the -naphthothiazole series and those of the quinoline series, J represents a member selected from the group consisting of a hydrogen atom and an alkyl group of the formula Cdilm+1 wherein d represents a positive integer from 1 to 2, Q represents a member selected from the group consisting of an alkyl group oi the formula CrHzdJfi wherein d represents a positive integer from. 1 to 2, and a monocyclic aryl group of the benzene series, and J and Q together represent the non-metallic atoms necessary to complete an organic basic nucleus selected from the group consisting of those of the piperidyl series and those of the morpholinyl series.

8. A photographic gelatino-silver-halide developing-out emulsion sensitized with a supersensitizing combination of at least one meso-aryl carbocyanine dye selected vfrom those represented by the following general formula:

ZX il) wherein R and R1 each represents an alkyl group of the formula Cul-12H1 wherein n represents a positive integer from l to 2, D represents a monocyclic aryl nucleus of the benzene series, X represents an acid radical, and Z and Z1 each represents the non-metallic atoms necessary to complete a heterocyclic nucleus of the benzoselenazole series, and at least one hemicarbocyanine dye selected from those represented by the following general formula:

Rz /Za ,l X N o- LiL- N X( El wherein R2 represents an alkyl group of the formula Cul-Imp wherein n represents a positive integer of from l to2, L represents a methenyl group, X1 represents an acid radical, Z2 represents the non-metallic atoms necessary to complete an organic heterocyclic nucleus selected from those of the benzothiazole series, those of the benzoxazole series, those of the benzoselenazole series, those of the -naphthothiazole series and those of the quinoline series, J represents a member selected from the group consisting of a hydrogen atom and an alkyl group of the formula CaH2d+1 wherein d represents a positive integer from 1 to 2, Q represents a member selected from the group consisting of an alkyl group of the formula CsH2 z+1 wherein d represents a positive integer from 1 to 2, and a monocyclic aryl group of the benzene series, and J and Q together represent the non-metallic atoms necessary to complete an organic basic nucleus selected from the group consisting of those of the piperidyl series and those of the morpholinyl series.

9. A photographic gelatino-silver-halide developing-out emulsion sensitized with a supersensitizing combination of at least one meso-aryl carbocyanine dyeselected from those represented by the following general formula:

wherein R and R1 each represents an alkyl group of the formula CH2n+1 wherein n represents a. positive integer from l to 2, D represents a mo-nocyclic aryl nucleus of the benzene series, X represents an acid radical, and Z and Z1 each represents the non-metallic atoms necessary to complete a heterocyclic nucleus selected from those of the benzothiazole series, those of the -naphthothiazole series and those of the benzoselenazole series, and at least one hernicarbocyanine dye selected from those represented by the following general formula:

R2 ,ZA R5 J ,f I

/N o-oir=o-N XT Q wherein Re represents an alkyl group of the formula CnHznH wherein n is a positive integer of from 1 to 2, R3 represents a member selected from the group consisting of ahydrogen atom, a methyl group and an ethyl group, X1 represents an acid radical, Z2 represents the non-metallic atoms necessary to complete an organic heterocyclic nucleus selected from those of the benzothiazole series, those of the benzoxazole series, those of the 'benzoselenazole series, those of the -naphthothiazole series and those of the quinoline sc-ri'es, J represents a member selected from the group consisting of a hydrogen atom and an alkyl group of the formula Cdl-izan wherein d represents a positive integer from 1 to2, Q represents a member .selected from the group consisting of an alkyl group of the formula Cdl-12am wherein d represents a positive integer from 1 to 2, and a monocyclic aryl group of the benzene series, and J and Q together represent the nonmetallic atoms necessary to complete an organic basic nucleus selected from the group consisting of those of the piperidyl series and those of the morpholinyl series.

10. A photographic gelatino-silver-halide developing-out emulsion sensitized with a supersensitizing combination of at least one meso- Aaryl carbocyanine dye selected from those represented by the following genera-l formula:

wherein R and R1 eacjc` represents an alkyl group of the formula C`nH2u+1 wherein n represents a positive integer from 1 to 2, D represents a monccyclic aryl nucleus of the benzene series, X represents an acid radical, and Z and Z1 each represents the non-metallic atoms necessary to complete a heterocyclic nucleus of the benzothiazole series, and at least one hemicarbocyanine dye selected from those represented by the vfollowing general formula: v

wherein R2 represents an alkyl group of the formula CnH2n+1 wherein n is a positive integer of from 1 to 2, R3 represents a member selected from the group consisting of a hydrogen atom, a methyl group and an ethyl group, X1 represents an acid radical, Z2 represents the non-metallic atoms necessary to complete an organic heterocyclic nucleus selected from those of the benzothiazole series, those of the benzoxazole series, those of the benzoselenazole series, those of the B-naphthothiazole series and those of the quinoline series, J represents a member selected from the group consisting of a hydrogen atom and an alkyl group of the formula CaHvd+1 wherein d represents a positive integer from 1 to 2, Q represents a member selected from the group consisting of an alkyl group of the formula CdH2d+1 wherein d represents a positive integer from 1 to 2, and a monocyclic aryl group of the benzene series, and J and Q together represent the nonmetallic atoms necessary to complete an organic basic nucleus selected from the group consisting of those of the piperidyl series and those of the morpholinyl series.

11. A photographic gelatino-silver-halide deveioping-out emulsion sensitized with a supersensitizing combination of at least one mese-aryl carbocyanine -dye selected from those represent- 4ed by the following general formula:

wherein R and R1 each represents an alkyl group of the formula CnHzn+1 wherein n represents a positive integer from 1 to 2, D represents a monocyclic aryl nucleus ol the benzene series, X represents an acid radical, and Z and Z1 each represents the non-metallic atoms necessary to complete a heterocyclic nucleus of trie -naphthothiazole series, and at least one hemicarbccyanine dye selected from those represented by the following general formula:

wherein R2 represents an alkyl group of the formula MI-12H1 wherein n is a positive integer of from 1 to 2, R3 Arepresents a member selected from the 'group consisting of a hydrogen atom, a methyl group and an ethyl group, Xrrepresents an acid radical, Zz represents the non-nietallic atoms necessary t0 4complete an organic heterocyclic nucleus selected from those of the benzothiazole series, those of the benzoxazole series, those of the benzoselenazole series, those of the ,3-naphthothiazole series and those of the quinoline series, J represents a `member selected from the group consisting of a hydrogen atom and an alkyl group of the formula CfzH2a+1 wherein d represents a positive integer from l to 2, Q represents a member selected from the group consisting of an alkyl group of the formula Cdl-1211+: wherein d represents a positive integer from 1 and 2, and a monocyclic aryl group or the benzene series, and J and Q together represent the non-metallic atoms necessary to complete an organic basic nucleus selected from the group consisting of those of the piperidyl series and those of the morpholnyl Series.

12. A photographic gelatino-silver-halide developing-out emulsion sensitized with a supersensitizing combination of at least one meso-aryl carbocyanine dye selected from those represented by the following general formula:

bx Tt ,ZNV/ n N -C=CH--(=oute wherein R and R1 each represents an alkyl group ci the formula C1LH1111+1 wherein n represents a positive integer from 1 to 2, D represents a monocyclic aryl nucleus of the benzene series, X represents an acid radical, and Z and Z1 each represents the non-metallic atoms necessary to corn- `plete a heterocyclic nucleus of the benzoselenazole, and at least one hemicarbocyanine dye Selected from those represented by the following general formula:

H2 IZA Re ,I f/ /l N=CCU=CN X: 0.

wherein R2 represents an alkyl group oi the formula C11H2n+1 wherein n is a positive integer of from 1 to 2, R3 vrepresents a member selected from the group consisting of a hydrogen atom, a methyl group and an ethyl group, X1 represents an acid radical, Zz represents the non-metallic atoms necessary to complete an organic heterocyclic nucleus selected from those of the benzothiazole series, those of the benzoxazo-le series, those of the benzoselenazole series, those of the -naphlthothiazole series and those of the quinoline series, J represents a member selected from the group consisting of a hydrogen atom and an alkyl group of the formula CaHzaJfi `wlnerein d repre-- sents a positive integer from 1 to 2, Q represents a member selected from the group consisting of an alkyl group of the formula CaHza+1 whereind represents a positive integer from 1 to 2, and a, monocyclic aryl group of the benzene series, and J and Q together represent the non-metallic atoms necessary to complete an organic `basic nucleus selected from the group consisting of those of the piperidyl series and those of the morpholinyl series.

13. A photographic gelatino-si1verhalide developing-out emulsion sensitized with a supersensitizing combination of a 3,3-dirnethyl-9-phenylselenacaroooyanne salt and a 2- [2-(p-anisidino) propenyllbenzothiazole ethyl salt.

14. A photographic gelatino-silyer-halide developing-out emulsion sensitized with 3,3-dimethyl-9phenylselenacarbocyanine bromide and 2-[2- (p-anisidino) propenyllbenzothiaole ethiodide.

15. A photographic gelatino-silver-halide developing-out emulsion sensitized with a supersen- 'Ythiacarbocyanine salt and a 2-[2-(p-ohloroanilino) -l-butenyll--naphthothiazole methyl salt.

18. A photographic gelatino-silver-halide de- Veloping-out emulsion sensitized with a supersensitizing combination of 3,3dimethyl9phenyl thiacarbocyanine iodide and 2- [2-(p-ch1oroani- 20 lino) -l-butenyll--naphthothiazole methiodide.

BURT H. CARROLL- No references cited.

Certificate of Correction Patent No. 2,533,427 December 12, 1950 BUR-T H. CARROLL It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction as follows:

Columns 7 and 8, opposite example 13, under the heading Red Light Exposure, subheading Fog, for 0.5 read .05; column 7 lines 69 and 70, for. "benzothiaselenacarbocybocyanine" read @enzothaseZenacarboog/anine; column 10, lines 62 to 64, for that portion of the formula reading D l-CB read zCH column 17, line 18, for 3,3 read 3,3; line 20, for benzothiaole read benzothiazole and that the said Letters Patent should be read as corrected above, so that the same may conform to the record of the ease in the Patent Oice.

Signed and sealed this 10th day of April, A. D. 1951.

THOMAS F. MURPHY,

Assistant Uommz'sszoner of Patents. 

1. A PHOTOGRAPHIC SILVER HALIDE EMULSION SENSITIZED WITH A SUPERSENSITIZING COMBINATION OF AT LEAST ONE MESO-ARYL CARBOCYANINE DUE SELECTED FROM THOSE REPRESENTED BY THE FOLLOWING GENERAL FORMULA: 